Surface active compounds



Patented Sept. 22, 1953 BEST AVAILABLE COPY WilliamEHaghesandEverettEFishenBartlesville, Okla, assignors to Cities Service Research and Development Company, New York, N. 2.. a corporation of New Jersey.

N Drawing. lication Jan 1951 ammoniu scisim. (class-ass) This-invention relates to new compositions of matter having surface active properties and more particularly to certain amine salts of substituted naphthalene sulfonic acids which are particularly useful in the breaking of emulsions such as oil field emulsions.

One of the most troublesome problems met with in crude oil production relates to the breaking of water-ln-oil emulsions formed in wells producing both water and brine. These emulsions are generally of two types. the first type a mechanically cut emulsionywhich is usually formed in the well by-faulty pump n q ipment. the other type being a gas-cut emulsion. the formation of which is aided by the emulsifying action of certain asphaltenes and other chemical emulsifiers present in the crude oil. The emulsion commonly encountered is a mixture of both of these types, and its properties will vary from well to well, and even from day to day in the same well. Unless these emulsions can be effectively and completely broken; the oil content is lost. It is also desirable thatthe emulsion bebroken asrapidly as possible, in order to keep the size and number of settling tanks to a minimum.

There are apparently two phases of an emulsion resolving problem. The first involves a surface phenomenon in which the oil film surrounding the water particles of micron size is weakened, allowing the particles to coalesce into larger droplets. T This-'bhase will be hereinafter referred to asthe emulsion breaking step. The other phase involves the splitting of the broken emulsion into separate oil and water phases. This phase will be referred to as the.

water separation step.

It-will be evident from the foregoingthat the ideal emulsion resolving agent. must beeffective to break both'm'echanical-cut and gas-cut emulsions with substantially equal facility. must rap idly break the emulsion. and must be effective in causing rapid water separation from the broken emulsion. The agent must also be effective in very small concentrations, in order to hold treating cost to a minimum.

It is an object of this invention to provide a series of compounds which will rapidly resolve emulsions of all types. giving rapid break and complete water separation. and which are ones-- tive in very small concentration.

It has been found that emulsion resolving agents which will accomplish the foregoing ob- Ject may be produced by reacting an aliphatic 2 ture of a polyethylene amine and an aliphatic amine, and neutralizing the reaction product with a propylated naphthalene sulfonic acid.

The intermediate aldehyde-amine reaction product is prepared by reacting from one to three mols of aldehyde with one mol of the mixed amines. The aldehyde may be acetaldehyde or any other higher aliphatic aldehyde. Formaldehyde should not be used since it apparently polymerizes under the conditions of the reaction. Generally. better results are obtained as the molecular weight of the aldehyde increases. The polyethylene amine may be diethylenetriamine, triethylenetetraminc, or tetraethylenepentamine, and should preferably be present in the mixed amines in the amount of from 25 to it per cent of the mixture, the remainder of the mixture being an alkyl amine, preferably, but not necessarily, of more than 4 carbon atoms. Products made utilizing only polyethylene amines are generally too oil-insoluble to be valuable as emulsion breakers, while products utilizing alhl amines alone. while oil-soluble, do not possess the desirable qualities of compositions made from the mixed amines. In treating certain emulsions, however, proportions outside of 25 to '25 per cent polyethylene amine are satisfactory.

The exact nature of the aldehyde-amine produot is not known, but is probably a mixture of a great number of difi'erent possible products of the reaction. It has been found that the conditions under which the products are reacted also makes a considerable difference in their properties. Thus. the amines and the aldehyde will react spontaneously when mixed. the temperature of the reaction mixture rising to 8090 C. This product, when neutralized, is not, however, a good breaking agent. In order to produce the so effective compositions, it has been found necessary to heat the reaction mixture to a temperature Just under its boiling point, which will vary. depending on the particular reactants. but which will be about 120-140 C. for mixtures using a long chain aldehyde such as heptaldehyde, and amines of six or more carbon atoms. The mixture should then be held at this temperature for a period of from one-half to one hour. If heated for more than one hour. the effectiveness of the finished composition is de- Aitenheating, the aldehyde-amine product is cooled, and it is neutralized to a methyl orange and point with prcpyiated naphthalene sulfenic aldehyde higher than formaldehyde with a mixas acid Prepared according to the directions given BEST AVAILABLE COPY a,ees,1as

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in whluhLZZiltn lsopropsl radieaisnd at a whole number from 1 to 4. Other acids used to more than four carbon atoms, heating the aldehide-amine mixture for a period of from about one halt to one hour at a temperature slightly below the boiling point 01 the mixture, and neutralizing the resultant product to a methyl orange end point with propylated naphthalene dpzhengentbemg mixed in an amount small butisumcient to causesubstantial resolution oi the emulsion, allowing the treated emulsion neutralize the aldehyde-amine p d 11 8 am (to settle into an oil phase and a water phase, and

stearic acid and petroleum green acidsnyielded piroducts iar interior in emulsion-breaking quali- In order that those skilled unit-he :art my more fully appreciate the wt. ourznew compositions, and their method of preparation. the following example is given. which is.illuszirative oi the preparation 01 atypical composi- Example Two mois (228 grams) otheptaldehyde, 1.25 mole (298 grams) or a commercial mixture of alkyl amines averaging twelve -carbonatoms to themolecule, and'OIIiS ml (142 grams) oitetraethylenepentamine were mixed and 'heated 'at about 1:40 C. torone hour. The'mixturewas then cooled,.and rive molsilomlgrams) oi propylated naphthalene sulionic acid was added. The neutrallzation'isaccompanied by the evolution of considerable heat, and no further heating was necessary'to bring the reaction to completion. The final product. when cooled, was 'a heavy viscous liquid, 1m viscous to inject directly into an oilfield gathering'line. Itwas therefore mixed with an equal volume or kerosene, the kerosene-product mixturebeing or a suitable viscosity for oil-neld'use.

The various :products produced as described above have been subiected'to various tests. in the field and in the laboratory. and have proven outstanding in breaking 'water in-oll emulsions, 'such as are'commonly met with in 'oil production. While the eflectiveness o! these compounds will vary-tromwell'towell depending upon the emulsion produced by the particular well, it'has' been found that-excellent'results have been obtained when the products are 'used in concentrations'as low as-floparts per million. and they are in general far superior to the bestdrthe commercial breakers now on the market, which are generally ineiiective at concentrations 'less than 250 parts permillion.

Having now described our inventiomwhat we claim as new and useful is:

1. The process-oi resolving emulsions'whichincludes mixing with a petroleum water-m-o'il emulsion a resolving agent consisting oi-aproduct prepared by mixing together'irom one to'three mole oi an aliphatic aldehydehavlng -more'than one carbon atom and one moi oi a mixture or a polyethylene amine and an altyl aminehaving separating .the oil from the water.

'2. 'lheprocess according to claim 1 in which ithe mixture stamina consists essentially of from aiomsmentdofifimcent oi a polyethylene amine,

'lflie hmeerbeingsnn alkyl amine oi more than tom carben'atom.

.3. Thaprocess of resolving emulsions which inmludes with a petroleum water-in-oil emulsion a resolving agent consisting oi a produdt'prepared by mixing one mol of heptaldehyde and about one mole of a mixture oi amines containingitromzzfi percent to percent oi'a polyethylene-amine, the rbalance being a 'mixture =of alkyl averaging twelve --carbon atoms to the moiecule heating the aldehyde-amine mixtureiorm. neriodzoidrom one-halt to one hourat a temperature of from ito C. and neuezesultantproductltoa methyl orange en'd :pcint mith :propyiatedmaphthalene :sulionic acid,"the amtbeing mixed inan amount :small bittaumcient to :causezubstantial resolution oi the emulsion, allowing the rtreated remulsion to settle-into mioll phaserand awater'phase, and

- oilirom'therwater.

nrresolvingfiemulsions which includes mixing with a metroleum water-in-oil emuisionlniresolvingsagentlconsisting of a productpreparedbyznixingtwn'mois:oiiheptaldehyde, one and .one quartermnls'ni :a-mixture .0: alkyl amines 'avemging twelve carbon atoms t0 the molemile, and three quarters-.012. mol :of tetraethylenepentamine, heating .the aldehyde-amine mixtureiioria period'oiahoutpne hour atea tem perature :01 :about :140' :C., .and neutralizing the resultant product to :a methyl orange end point with pro :naphthalene 'sulfonic acid, the agent being mixed in an amount small but suincient'tonausezsubstantial resolution-.01 =the .emulslommltowingthe treatedwmulsion-to settle into a water-phase, and separating themil iromithewater.

WILLIAM B.'HUGHES. :EVERE'IIB. FISHER.

' MM"fli0d:ln-fl18.fl1e .0! this patent UNITED STATES PATENTS Number Name Date 2,083,225 De Groote June 8,1937 2223335 Daniels et a1 Dec. '3, 1940 $821,486 "Liberthson June .8, 1943 

1. THE PROCESS OF RESOLVING EMULSIONS WHICH INCLUDES MIXING WITH A PETROLEUM WATER-IN-OIL EMULSION A RESOLVING AGENT CONSISTING OF A PRODUCT PREPARED BY MIXING TOGETHER FROM ONE TO THREE MOLS OF AN ALIPHATIC ALDEHYDE HAVING MORE THAN ONE CARBON ATOM AND ONE MOL OF A MIXTURE OF A POLYETHYLENE AMINE AND AN ALKYL AMINE HAVING MORE THAN FOUR CARBON ATOMS, HEATING THE ALDEHYDE-AMINE MIXTURE FOR A PERIOD OF FROM ABOUT ONE HALF TO ONE HOUR AT A TMEPERATURE SLIGHTLY BELOW THE BOILING POINT OF THE MIXTURE, AN NEUTRALIZING THE RESULTANT PRODUCT TO A METHYL ORANGE END POINT WITH PROPYLATED NAPHTHALENE SULFONIC ACID, THE AGENT BEING MIXED IN AN AMOUNT SMALL BUT SUFFICIENT TO CAUSE SUBSTANTIAL RESOLUTION OF THE EMULSION, ALLOWING THE TREATED EMULSION TO SETTLE INTO AN OIL PHASE AND A WATER PHASE, AND SEPARATING THE OIL FROM THE WATER. 